TW202021911A - Processing system and processing method for liquid containing tetraalkylammonium hydroxide - Google Patents

Abstract

A system for processing a liquid containing a tetraalkylammonium hydroxide, having a high-pressure reverse osmosis membrane device that concentrates, on the concentrate side, a processing target liquid containing the tetraalkylammonium hydroxide, and a line that supplies the processing target liquid that has been concentrated by the reverse osmosis membrane device to an evaporator that further concentrates the liquid.

Description

Treatment system and treatment method of tetraalkylammonium hydroxide containing liquid

The present invention relates to a treatment system and a treatment method for tetraalkylammonium hydroxide containing liquid.

In the photolithography process in the manufacturing field of semiconductor devices such as semiconductor elements and liquid crystal displays, positive photoresists (hereinafter, also referred to as resists) are mainly used. The developer mostly uses a solution containing tetraalkylammonium hydroxide (TAAH) (TAAH developer). Tetramethylammonium (TMAH) is generally used as TAAH. The method of using the TMAH developer is to coat a resist on the substrate to form a resist film, and then expose the resist film through a photomask to make an alkali solution-soluble resist part. A resist pattern is formed by dissolving and removing the resist part (development step) with a highly alkaline TMAH developer. TMAH developer generally uses a TMAH aqueous solution with a TMAH concentration of 2.38% by mass. In the case of a positive resist, through the development step, the solubility of the exposed part to the TMAH developer increases and can be dissolved and removed, and the resist in the unexposed part remains to form a resist pattern. Then, the TMAH developer that reacts with the resist on the substrate is cleaned with pure water or the like. As a result, the development waste liquid becomes a mixed liquid of the TMAH of the developer, the dissolved resist, and water.

Because TMAH is designated as a poison, drainage treatment is required, and the corresponding treatment is carried out in the factory. Therefore, the processing demand and importance of the photoresist containing TMAH containing waste developing solution (hereinafter also referred to as waste developing solution) have increased. In some factories, evaporators are used to concentrate the above-mentioned developing waste liquid to reduce the volume, and deal with industrial waste or collect valuables for off-company transactions. In addition, TMAH can also be recovered and reused through biological treatment and treatment using electrodialysis (ED) and resin (for example, ion exchange resin). In addition, the technology of concentration by supplying TMAH-containing drain water to a reverse osmosis (RO) membrane under pressure (please refer to Patent Document 1) and the use of a nanofiltration (NF) membrane to treat the photoresist developing waste liquid containing photoresist and TMAH The technology of separating the photoresist on the concentration side and separating the TMAH on the transmission side (please refer to Patent Document 2) and the like are well-known. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 60-118282 Patent Document 2: Japanese Patent Laid-Open No. 11-192481

In recent years, the processing volume of TAAH waste liquid has increased due to the increase in the number of development steps and the need for TAAH drainage even if it contains only a small amount of TAAH, and the concentration processing volume using an evaporator has increased. Therefore, the concentration capacity of the existing evaporator is insufficient, and countermeasures are needed. When a separation membrane is used to concentrate the development waste liquid such as TAAH-containing liquid, there is a problem that the membrane is blocked (occluded) by the resist. If the membrane is clogged, it must be replaced with a new membrane. In addition, in recent years, RO membranes with high rejection rates (high-pressure RO membranes, etc.) have been on the market. When this RO membrane is used, TAAH and resist can be treated with high rejection rates. However, the high-pressure RO membrane has a problem of blocking the membrane due to the resist in the conventional RO (medium to ultra-low pressure RO) membrane.

The subject of the present invention is to provide a TAAH-containing liquid processing system and TAAH-containing liquid processing method, which reduce the concentration load of the evaporator, so even if the TAAH-containing liquid increases, it is possible to process the TAAH-containing liquid without adding an evaporator. At the same time, the subject of the present invention is to provide a TAAH-containing liquid processing system and a TAAH-containing liquid processing method, which enables the RO film used as a concentration load reduction device related to the evaporator to be produced by the resist dissolved in the developer The processing capacity is reduced due to the clogging of the hole or the state cannot be processed.

The above-mentioned problems of the present invention are solved by the following means. [1] A tetraalkylammonium hydroxide-containing liquid treatment system, which has: a high-pressure reverse osmosis membrane device that concentrates the treated liquid containing tetraalkylammonium hydroxide on the concentration side; and a pipeline that is supplied to the further concentration The evaporator of the liquid to be treated concentrated by this reverse osmosis membrane device. [2] The tetraalkylammonium hydroxide-containing liquid treatment system described in [1] has a cleaning system that cleans the aforementioned reverse osmosis membrane device with a cleaning liquid containing tetraalkylammonium hydroxide. [3] The tetraalkylammonium hydroxide-containing liquid treatment system as described in [1] or [2], wherein the aforementioned tetraalkylammonium hydroxide-containing liquid treatment system can form part of the treatment system containing the aforementioned reverse osmosis membrane The circulation system constituted by the device, and by circulating the cleaning solution containing tetraalkylammonium hydroxide in the circulation system, the circulation system can be used as a cleaning system for cleaning the reverse osmosis membrane of the aforementioned reverse osmosis membrane device. [4] The treatment system for tetraalkylammonium hydroxide containing liquid as described in [3], wherein the aforementioned treatment system for tetraalkylammonium hydroxide containing liquid has: (a-1) Liquid tank for storing liquid containing tetraalkylammonium hydroxide; (b-1) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-1) A reverse osmosis membrane device, which is connected to the other end of the liquid supply pipe; (d-1) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-1) Concentrated water return pipe, which is connected to the concentrated water pipe and supplies the concentrated water of the reverse osmosis membrane device to the liquid tank; (f-1) Permeate water pipe, one end of which is connected to the permeation side of the aforementioned reverse osmosis membrane device; (g-1) Thin tetraalkylammonium hydroxide wastewater treatment equipment, connected to the other end of the permeate pipe; and (h-1) The permeated water return pipe is connected to the permeated water pipe and supplies the permeated water of the reverse osmosis membrane device to the liquid tank, The aforementioned cleaning system is to supply fresh tetraalkylammonium hydroxide solution to the aforementioned tank, and make the fresh solution of tetraalkylammonium hydroxide form the aforementioned (a-1) to (d-1) and (e-1) The circulation system and the two circulation systems formed by the aforementioned (a-1) to (c-1), (f-1) and (h-1) are circulated, thereby cleaning the reverse osmosis membrane device with Reverse osmosis membrane system. [5] The treatment system for tetraalkylammonium hydroxide containing liquid as described in [3], wherein the aforementioned treatment system for tetraalkylammonium hydroxide containing liquid has: (a-2) Liquid tank for storing liquid containing tetraalkylammonium hydroxide; (b-2) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-2) A reverse osmosis membrane device connected to the other end of the liquid supply pipe; (d-2) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-2) Concentrated water return pipe, which is connected to the concentrated water pipe and supplies the concentrated water of the reverse osmosis membrane device to the liquid tank; (f-2) Permeate water piping, one end of which is connected to the permeation side of the aforementioned reverse osmosis membrane device; (g-2) The permeated water tank is arranged in the middle of the permeated water pipe; (h-2) Thin tetraalkylammonium hydroxide drainage treatment equipment, connected to the other end of the permeate pipe; and (i-2) The permeated water return pipe is connected to the permeated water pipe between the permeated water tank and the thin tetraalkylammonium hydroxide drainage treatment equipment and supplies the permeated water of the reverse osmosis membrane device to the liquid tank , The aforementioned cleaning system supplies fresh tetraalkylammonium hydroxide liquid to the aforementioned liquid tank, and makes the fresh tetraalkylammonium hydroxide liquid form the aforementioned (a-2) to (d-2) and (e-2) Circulation system and the two-circulation system formed by the aforementioned (a-2) to (c-2), (f-2), (g-2) and (i-2), thereby cleaning the aforementioned The reverse osmosis membrane device has a reverse osmosis membrane system. [6] The treatment system for tetraalkylammonium hydroxide containing liquid as described in [3], wherein the aforementioned treatment system for tetraalkylammonium hydroxide containing liquid has: (a-3) Liquid tank for storing liquid containing tetraalkylammonium hydroxide; (b-3) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-3) Reverse osmosis membrane device (Y), connected to the other end of the liquid supply pipe; (d-3) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-3) Concentrated water return pipe, which is connected to the concentrated water pipe and supplies the concentrated water of the reverse osmosis membrane device (Y) to the liquid tank; (f-3) Permeate water piping (P), one end of which is connected to the permeation side of the aforementioned reverse osmosis membrane device (Y); (g-3) The permeated water tank is arranged in the middle of the permeated water pipe (P); (h-3) Thin tetraalkylammonium hydroxide drainage treatment equipment, connected to the other end of the permeate pipe (P); (i-3) The permeated water return pipe (I) is connected to the permeated water pipe (P) between the reverse osmosis membrane device (Y) and the permeated water tank and supplies the reverse osmosis membrane device (Y) Permeate water to the aforementioned liquid tank; (j-3) The permeated water concentration tank is arranged in the middle of the permeated water return pipe (I); (k-3) Another permeated water return pipe (II), which is branched from the permeated water pipe (P) between the permeated water tank and the thin tetraalkylammonium hydroxide drainage treatment facility, and is connected to The permeated water return pipe (I) between the reverse osmosis membrane device (Y) and the permeated water concentration tank; (l-3) Another reverse osmosis membrane device (Z) is arranged in the middle of the other permeated water return pipe (II); and (m-3) Another permeated water piping (Q), which connects the permeate side of the other reverse osmosis membrane device (Z) and the aforementioned thin tetraalkylammonium hydroxide drainage treatment equipment, The cleaning system supplies concentrated water (X) that concentrates the permeated water of the reverse osmosis membrane device (Y) by the other reverse osmosis membrane device (Z) to the liquid tank, and makes the concentrated water (X) The circulatory system formed by the aforementioned (a-3) to (d-3) and (e-3) and the aforementioned (a-3) to (c-3), (f-3), (i-3) and ( j-3) A system that circulates in the two-circulation system of the formed circulation system, thereby cleaning the reverse osmosis membrane of the aforementioned reverse osmosis membrane device. [7] The treatment system for tetraalkylammonium hydroxide containing liquid as described in [3], wherein the aforementioned treatment system for tetraalkylammonium hydroxide containing liquid has: (a-4) Liquid tank for storing liquid containing tetraalkylammonium hydroxide; (b-4) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-4) A reverse osmosis membrane device connected to the other end of the liquid supply pipe; (d-4) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-4) The concentrated water tank is arranged in the middle of the concentrated water piping; (f-4) The concentrated water return pipe is connected to the concentrated water pipe located between the reverse osmosis membrane device and the concentrated water tank and supplies the concentrated water of the reverse osmosis membrane device to the liquid tank; (g-4) Concentrated water permeation piping, which is branched from the concentrated water piping located on the downstream side of the concentrated water tank and connected to the concentrated water return piping; (h-4) The nanofiltration device is arranged in the middle of the concentrated water permeation pipe; (i-4) A nanofiltration permeable water tank is arranged in the middle of the concentrated water permeation pipe and stores the permeated water of the aforementioned nanofiltration device; (j-4) A nanofiltration concentrated water pipe, one end of which is connected to the concentration side of the nanofiltration device and supplies the concentrated water of the nanofiltration device to the evaporator; (k-4) Permeate water piping, one end of which is connected to the permeation side of the aforementioned reverse osmosis membrane device; (l-4) Thin tetraalkylammonium hydroxide drainage treatment equipment, connected to the other end of the permeated water pipe; and (m-4) The permeated water return pipe is connected to the permeated water pipe and supplies the permeated water to the aforementioned liquid tank, The aforementioned cleaning system is to supply fresh tetraalkylammonium hydroxide liquid to the aforementioned liquid tank, and make the fresh tetraalkylammonium hydroxide liquid from the aforementioned (a-4) to (e-4) and (f-4) to (i-4) Circulate in the two-circulation system formed by the circulation system and the circulation system formed by the aforementioned (a-4) to (c-4), (k-4) and (m-4), thereby cleaning the aforementioned The reverse osmosis membrane device has a reverse osmosis membrane system. [8] The treatment system for tetraalkylammonium hydroxide containing liquid as described in [3], wherein the aforementioned treatment system for tetraalkylammonium hydroxide containing liquid has: (a-5) Liquid tank for storing liquid containing tetraalkylammonium hydroxide; (b-5) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-5) Reverse osmosis membrane device (Y), connected to the other end of the liquid supply pipe; (d-5) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-5) Concentrated water return piping, connected to the concentrated water piping and supplying the concentrated water of the reverse osmosis membrane device (Y) to the liquid tank; (f-5) Permeate water pipe (P), one end of which is connected to the permeate side of the aforementioned reverse osmosis membrane device (Y); (g-5) Permeated water tank, arranged in the middle of the permeated water pipe (P); (h-5) Dilute tetraalkylammonium hydroxide drainage treatment equipment, arranged at the other end of the permeated water pipe (P); (i-5) The permeated water return pipe (I) is connected to the permeated water pipe (P) between the reverse osmosis membrane device (Y) and the permeated water tank and supplies the reverse osmosis membrane device (Y) Permeate water to the aforementioned liquid tank; (j-5) The permeated water concentration tank is arranged in the middle of the permeated water return pipe (I); (k-5) Another permeated water return pipe (II), which is branched from the permeated water pipe (P) between the permeated water tank and the thin tetraalkylammonium hydroxide drainage treatment facility, and is connected to The permeated water return pipe (I) between the reverse osmosis membrane device (Y) and the permeated water concentration tank; (l-5) Another reverse osmosis membrane device (Z) is arranged in the middle of the other permeated water return pipe (II); (m-5) The nanofiltration device is arranged in the middle of the other permeated water return pipe (II) and treats the concentrated water of the other reverse osmosis membrane device (Z); (n-5) Another permeate pipe (Q), which connects the permeate side of the other reverse osmosis membrane device (Z) and the aforementioned thin tetraalkylammonium hydroxide drainage treatment equipment; and (o-5) Nanofiltration concentrated water piping, which connects the concentration side of the nanofiltration device and the other permeated water piping (Q), The cleaning system supplies the permeated water of the reverse osmosis membrane device (Y) through the other reverse osmosis membrane device (Z) to concentrate and further permeate the permeated water treatment water of the nanofiltration device to the liquid tank, and The aforementioned permeate treated water is in the circulation system formed by the aforementioned (a-5) to (d-5) and (e-5) and the aforementioned (a-5) to (c-5), (f-5) and (i-5) A system that circulates in the two-circulation system of the formed circulation system, thereby cleaning the reverse osmosis membrane of the aforementioned reverse osmosis membrane device. [9] The tetraalkylammonium hydroxide-containing liquid treatment system as described in any one of [4] to [8] has: A measuring device that measures the resist concentration of the cleaning solution supplied from the liquid tank by the cleaning system; and The cleaning state detection device detects the cleaning state based on the aforementioned measured resist concentration. [10] A treatment method for tetraalkylammonium hydroxide containing liquid, which has: When the liquid to be treated containing tetraalkylammonium oxide is concentrated by an evaporator, a concentration step of concentrating the liquid to be treated from the liquid to be treated on the concentration side by a reverse osmosis membrane device arranged in the front stage of the evaporator, The treatment method of the aforementioned tetraalkylammonium hydroxide containing liquid includes: in response to the clogging of the reverse osmosis membrane of the aforementioned reverse osmosis membrane device, the use of fresh tetraalkylammonium hydroxide liquid and/or permeate water generated by the reverse osmosis membrane device The cleaning step of cleaning the reverse osmosis membrane.

According to the TAAH-containing liquid processing system and processing method of the present invention, the concentration load of the evaporator can be reduced by arranging the RO membrane device as the pre-concentration device in the front stage of the evaporator. Therefore, it is not necessary to add an evaporator, but can realize the concentration treatment of the TAAH-containing liquid of the above amount by the existing evaporator. In addition, by using the new TAAH solution and/or at least using the permeated water produced by the reverse osmosis membrane device to process the treated solution to clean the pore clogging caused by the resist produced on the water side of the RO membrane of the former concentration device, it can reduce It is cost-effective and efficient to remove and recover from the reduced processing capacity or unprocessable state caused by hole clogging.

The above and other features and advantages of the present invention can be better understood from the following description and appended drawings.

Hereinafter, a preferred embodiment (Embodiment 1) of a processing system for a developing waste liquid as a processing system for the TAAH-containing liquid of the invention will be described with reference to FIG. 1. As shown in FIG. 1, the processing system 1 (1A) of the development waste liquid has a pipeline supplied to the evaporator 11, and the evaporator 11 concentrates the processed liquid as the development waste liquid generated in the photolithography step. The treated liquid contains TAAH and photoresist. In the description with reference to Figures 1 to 9 below, although the treatment liquid contains TMAH and photoresist as TAAH as an example, it can be said that the treatment liquid contains TAAH other than TMAH. The same time. In addition, in addition to using resists for light exposure, photoresists also include resists exposed by energy beams such as electron beams and X-rays. The evaporator 11 has a high-pressure reverse osmosis membrane (RO membrane) device 21 for concentrating the non-treated liquid at the front stage. Preferably, the concentrated water produced by the RO membrane device 21 is concentrated by the evaporator 11.

Specifically, it has a liquid tank 31 for storing (storing) the non-processing liquid used in the manufacturing process of the semiconductor device. The RO membrane device 21 is connected to the liquid discharge side of the liquid tank 31 through a liquid supply pipe 32 for supplying the liquid to be processed. One end of the liquid supply pipe 32 is connected to the discharge side of the liquid tank 31, and the water supply side of the RO membrane device 21 is connected to the other end of the liquid supply pipe 32. The liquid transfer device 33 that transfers the liquid in the pipe to the RO membrane device 21 side is preferably arranged in the liquid supply pipe 32. The liquid delivery device 33 only needs to deliver the liquid, and a general pump can be used, preferably, for example, a pressure delivery pump. In this way, the liquid supply system 30 to be processed is constructed. This to-be-processed liquid supply system 30 also becomes the cleaning liquid supply system 30A mentioned later.

The evaporator 11 is connected to the concentration side 21C (the concentrated water discharge side) of the RO membrane device 21 through the concentrated water pipe 41. Specifically, one end side of the concentrated water pipe 41 is connected to the concentration side 21C of the RO membrane device 21, and the supply side of the evaporator 11 is connected to the other end side of the concentrated water pipe 41. That is, there is a concentrated water pipe 41 as a pipeline for supplying concentrated water concentrated by the RO membrane device 21 to the evaporator 11. A concentrated water tank 42 for temporarily storing concentrated water should be arranged in the middle of the concentrated water piping 41. In addition, the concentrated water conveying device 43 that conveys the concentrated water in the concentrated water tank 42 to the supply side of the evaporator 11 is preferably arranged in the concentrated water piping 41 between the concentrated water tank 42 and the evaporator 11.

On the other hand, the concentrated water return pipe 46 that supplies concentrated water to the liquid tank 31 is connected to the concentrated water pipe 41 between the RO membrane device 21 and the concentrated water tank 42. The cooler 91 is preferably arranged in the concentrated water return pipe 46. The liquid to be treated heated by the liquid conveying device 33 is cooled by the cooler 91. Therefore, the temperature of the liquid stored in the liquid tank 31 can be suppressed from excessively high. The cooler 91 may be water-cooled or use other refrigerants. The temperature of the concentrated water should preferably be cooled to normal temperature (20°C±15°C (JIS Z8703)), more preferably about 15 to 25°C. The concentrated water return pipe 46 preferably has a valve 47 near the branch point from the concentrated water pipe 41. In addition, the concentrated water piping 41 preferably has a valve 48 between the branch point and the concentrated water tank 42. When processing the liquid to be processed, the valves 47 and 48 can be opened by adjusting their opening degrees. On the other hand, during cleaning, valve 47 is opened and valve 48 is closed. In this way, the concentrated water return system 40 (40A) (40A) of the concentrated water returning to the liquid tank 31 through the liquid tank 31 through the cleaning liquid supply system 30A, the concentration side 21C of the RO membrane device 21, the concentrated water pipe 41, and the concentrated water return pipe 46 Circulatory system).

Preferably, one end of the permeate pipe 61 is connected to the permeate side 21T of the RO membrane device 21, and the other end of the permeate pipe 61 is connected to the thin TAAH drainage treatment facility 93. The thin TAAH drainage treatment equipment 93 is a device that makes the thin TAAH drainage harmless by biological treatment, adsorption and detoxification. The permeated water tank 62 should be placed in the middle of the permeated water piping 61. In addition, the permeated water conveying device 63 that transmits the permeated water in the permeated water tank 62 should be placed in the permeated water piping 61 between the permeated water tank 62 and the thin TAAH drainage treatment equipment 93 . The permeated water delivery device 63 only needs to deliver liquid, and a general pump can be used, and it is preferable to use, for example, a pressure delivery pump. In addition, the permeated water pipe 61 may not be connected to the thin TAAH drainage treatment facility 93, and the liquid flowing through the permeated water pipe 61 may be reused in the semiconductor manufacturing step. In addition, the liquid made harmless by the thin TAAH drainage treatment facility 93 can also be reused in the semiconductor manufacturing process.

On the other hand, the permeated water return pipe 66 that supplies permeated water to the liquid tank 31 is connected to the permeated water pipe 61 between the RO membrane device 21 and the permeated water tank 62. The permeated water return pipe 66 preferably has a valve 67 near the branch point of the permeated water pipe 61. In addition, the permeated water pipe 61 preferably has a valve 68 between the branch point and the permeated water tank 62. When processing the liquid to be processed, the valve 68 is opened and the valve 67 is closed. On the other hand, during cleaning, the valve 67 is opened oppositely and the valve 68 is closed. In this way, the permeated water return system 60 (60A) (60A) that returns to the liquid tank 31 from the liquid tank 31 through the cleaning liquid supply system 30A, the permeate side 21T of the RO membrane device 21, the permeated water pipe 61, and the permeated water return pipe 66 (the permeate side Circulatory system). This can be used as a cleaning system described later.

In the RO film 21F of the RO film device 21, the removal rate of TMAH should be 99.5% by mass or more and the removal rate of resist should be 99.5% by mass or more. TMAH removal rate is defined by [1-(permeated water TMAH concentration/supply water TMAH concentration)]×100%, and the resist removal rate is defined by [1-(permeable water resist concentration/supply water resist Concentration)]×100%. Each concentration is on the water supply side 21S and the permeation side 21T of the RO membrane device 21. Samples are collected by the sampling pipes 34 and 64, and then the TMAH concentration is measured using a titration device or an electrophoresis device and the resist concentration is measured using the absorbance indicator value of an absorbance photometer. In addition, the above-mentioned RO membrane device 21 has a mechanism for discharging water (concentrated water) such as concentrated salts and impurities, and by discharging the concentrated water, it is possible to suppress excessive increase in the salt concentration on the pressurized side and the generation of insoluble substances (scales) on the membrane surface. ) Wait and continuously produce permeated water.

In addition, it is preferable that the RO membrane 21F is resistant to a strong alkaline solution such as a developing waste solution (for example, pH 12 or higher) as the treated liquid. Such a high-pressure RO membrane can be a polyamide RO membrane as an example. Specifically, SWC 5 (trade name) manufactured by Nitto Denko Corporation can be cited as an example. The manufacturer of this RO membrane recommends a common pH range of pH 2 to 11 and pH 1 to 13 during cleaning. However, it is confirmed that even if the continuous test (3620 hours (about 150 days) of continuous operation) is carried out in which the water to be treated is supplied with approximately pH 12 There is no change, so there is no problem in using it as a film.

Since the processing system 1 for the above-mentioned developing waste liquid has an RO membrane device 21 in the front stage of the evaporator 11, the RO membrane device 21 can concentrate the liquid to be treated. For example, when processing the liquid to be processed, when the TMAH concentration of the liquid to be processed is 1% by mass, the RO membrane device 21 is concentrated three times to 3% by mass, and is further concentrated by the evaporator 11 to 25% by mass. That is, the concentrated water volume of the evaporator is 1/3 of the conventional one. In this way, the amount of water concentrated by the evaporator 11 is reduced, and therefore the treatment amount of the liquid to be treated that can be concentrated by one evaporator can be increased. As a result, the processing volume of the liquid to be treated can be increased without adding the evaporator 11 related to the cost of the device, so that the liquid to be treated can be concentrated efficiently at low cost.

When the RO membrane 21F of the aforementioned RO membrane device 21 concentrates and treats the liquid to be treated containing photoresist for a long time, the photoresist adheres to the water supply side 21S of the RO membrane 21F and the amount of permeated water decreases. At this time, use at least TMAH fresh liquid (unused liquid containing TMAH) and/or permeate water to clean the water supply side 21S of the RO membrane 21F of the RO membrane device 21 by processing the treated liquid by the RO membrane device 21 The cleaning system 100 (100A) is effective. That is, the cleaning system 100 can remove the resist adhering to the concentrated side 21C of the RO membrane 21F. As a result, the reduced permeation flux during the treatment of the liquid to be treated can be recovered, and therefore the reduction in the amount of permeated water can be recovered. The above-mentioned cleaning liquid may preferably contain TMAH for use. Normally, since what adheres to the water supply side of the RO film 21F is mainly a resist that is dissolved by development, the resist is dissolved and easily removed by containing TMAH in the cleaning solution.

Next, the cleaning system will be described. In the case of the processing system 1A of the above-mentioned developing waste liquid, the washing system 100A is composed of the washing liquid supply system 30A, the concentrated water return system 40A, and the permeated water return system 60A, which are common to the liquid supply system 30 described above. The aforementioned cleaning liquid supply system 30A has the same structure as the aforementioned liquid supply system 30 to be processed. The concentrated water return system 40A is connected to the RO membrane device 21 and passes into the liquid tank 31, and is composed of a concentrated water pipe 41 and a concentrated water return pipe 46. In addition, the concentrated water piping 41 is connected from the concentration side 21C of the RO membrane device 21 to the part connecting the concentrated water return piping 46. The cooler 91 is preferably arranged in the concentrated water return pipe 46. In addition, the permeated water return system 60A is composed of: a part of the permeated water pipe 61 connected to the permeate side of the RO membrane device; and the permeated water return pipe 66 that is branched from the permeated water pipe 61 and passed into the liquid tank 31. Furthermore, the permeated water pipe 61 is connected from the permeate side 21T of the RO membrane device 21 to the portion connected to the permeated water return pipe 66. In this way, the cleaning system 100A becomes a full-volume circulation system of the TMAH fresh liquid supplied to the liquid tank 31 through the concentrated water return system 40A and the permeated water return system 60A centering on the liquid tank 31.

Next, the measuring machine of the processing system 1 (1A) of the developing waste liquid will be explained. The liquid sampling pipe 34 for taking the liquid flowing in the pipe is preferably connected between the liquid conveying device 33 and the RO membrane device 21, and the permeation valve 35 is connected to the liquid supply pipe 32. In addition, in the liquid supply pipe 32, the pressure gauge 81 is preferably arranged between the liquid collection pipe 34 and the RO membrane device 21. The concentrated water collection piping 44 that collects the liquid flowing in the piping is preferably connected to the concentrated water piping 41 between the RO membrane device 21 and the concentrated water tank 42, and the valve 45 is preferably arranged in the concentrated water collection piping 44. In addition, in the concentrated water piping 41, the pressure gauge 82 is preferably arranged between the branch point of the concentrated water collection piping 44 and the RO membrane device 21. In addition, in the concentrated water piping 41, the flow meter 86 is preferably arranged between the branch point of the concentrated water return piping 46 and the concentrated water piping 41 and the concentrated water tank 42. In the concentrated water return pipe 46, the flow meter 87 is preferably arranged between the branch point of the concentrated water return pipe 46 and the concentrated water pipe 41 and the cooler 91. The permeated water collection piping 64 for taking the liquid flowing through the pipe should be connected to the permeated water piping 61 between the RO membrane device 21 and the permeated water tank 62, and the valve 65 should be arranged in the permeated water collection piping 64. In addition, in the permeated water piping 61, the flow meter 88 is preferably arranged between the permeated water collection pipe 64 and the permeated water tank 62.

A pH meter, a TMAH concentration meter, a resist absorbance measuring device, etc. can be connected to the liquid collection pipe 34, the concentrated water collection pipe 44, and the permeated water collection pipe 64 (hereinafter also referred to as collection pipe).

The liquid system flowing through the liquid supply pipe 32, the concentrated water pipe 41, and the permeated water pipe 61 can be opened by the valves 35, 45, 65 arranged in the respective collection pipes 34, 44, 64, and the respective collection pipes 34, 44 , 64 to obtain samples. Usually, each valve 35, 45, 65 is closed first, and then opened when a sample is taken. The pressure gauges 81, 82, and 83 can be general pressure gauges, digital pressure gauges, diaphragm pressure gauges, etc., and the diaphragm pressure gauge is preferred from the viewpoint of high alkali resistance and high pressure. Take the SC type (trade name) manufactured by Nagano Keiki Co., Ltd. as an example. Each of the flow meters 86, 87, 88 can use an area flow meter, an impeller type flow meter, an electromagnetic flow meter, etc., and from the viewpoint of a simple structure and ensuring that the material is resistant to pH, the area flow meter is preferred. Such a flowmeter may be PURGEMETER (trade name) manufactured by Tokyo Metering Co., Ltd. (stock).

Hereinafter, the main components will be described. The evaporator 11 is a device having a function of actively evaporating solids or liquids by reducing pressure. Specifically, it is a device that makes the inside of an evaporator heated by a heat source such as steam easy to evaporate the water in the drain by reducing the pressure with a vacuum pump or the like, and is a device generally used by volume reduction of the drain. Take the VVCC enrichment device (trade name) manufactured by SASAKURA Co., Ltd. as an example.

The above-mentioned RO membrane device 21 is not particularly limited. It can be any of high-pressure, medium-pressure, low-pressure, and ultra-low-pressure RO membrane devices, but it is better to use the above-mentioned TMAH with a removal rate of 99.5 mass% or more and A high-pressure RO film with a photoresist removal rate of 99.5% by mass or more.

The liquid tank 31 stores the photoresist containing developing waste liquid or cleaning liquid as the liquid to be processed. The photoresist contains a mixed solution of TMAH, the dissolved photoresist, and water of the developing waste liquid. In addition, it also contains the liquid from the photoresist containing the developing waste liquid. The liquid from the photoresist containing the developing waste liquid, specifically, for example, concentrated water produced by the RO membrane device 21, permeated water produced by the RO membrane device 21, and the like.

In the liquid conveying device 33 that conveys the solution from the liquid tank 31 to the RO membrane device 21, in order to convey the developing waste liquid of the strong alkali solution, at least the flow path is preferably made of an alkali-resistant material. Take a high-pressure pump made of metal and alkali-resistant materials as an example. Take PROCESS PUMP (trade name) manufactured by NIKUNI Corporation (stock) as an example.

The concentrated water tank 42 is a tank that temporarily stores the concentrated water generated by the RO membrane device 21, and may include a liquid after washing when the RO membrane 21F is washed with a developer containing liquid. Therefore, it is best to have alkali resistance. In addition, the RO membrane 21F may be cleaned with the permeated water of the RO membrane device or the concentrated water of the RO membrane device.

The permeated water tank 62 is a tank that temporarily stores the permeated water generated by the RO membrane device 21. The concentration of the TMAH component of the permeated water in the tank is extremely low, and the permeated water conveying device 63 can be activated to immediately transport the permeated water in the tank to the thin TAAH drainage treatment equipment 93.

The liquid delivery device 33 preferably uses, for example, a pressure delivery pump. In order to transport the liquid to be treated containing the developing waste liquid of the strong alkali solution, at least the flow path or the internal parts of the pump should be made of alkali-resistant materials. Take PROCESS PUMP (trade name) manufactured by NIKUNI Corporation (stock) as an example.

For the concentrated water delivery device 43, it is preferable to use, for example, the same pressure delivery pump as the above-mentioned liquid delivery device 33.

The permeated water delivery device 63 preferably uses, for example, a pressure pump. In order to transport the permeated water of the alkaline solution, at least the flow path or the internal parts of the pump should be made of alkali-resistant materials. Take MAGNET PUMP (trade name) manufactured by IWAKI Corporation (stock) as an example.

Next, a description will be given of an example of a preferred method for processing waste development liquid in the waste development liquid processing system shown in FIG. 1. When processing the developing waste liquid, the developing waste liquid is supplied to the liquid tank 31, and then the developing waste liquid in the liquid tank 31 is sent to the RO membrane device 21 by the liquid conveying device 33. Preferably, the permeated water passing through the RO membrane 21F of the RO membrane device 21 is sent to the permeated water tank 62 through the permeated water pipe 61, and then the permeated water of the permeated water tank 62 is further sent to the thin TAAH drainage treatment equipment 93 by the permeated water conveying device 63. On the other hand, part of the concentrated water generated by the RO membrane device 21 is supplied to the concentrated water tank 42 through the concentrated water piping 41, and then sent to the evaporator 11 by the concentrated water conveying device 43 to be further concentrated. The remaining concentrated water returns to the liquid tank 31 from the concentrated water pipe 41 through the concentrated water return pipe 46. The ratio of the concentrated water returned to the liquid tank 31 and the concentrated water supplied to the concentrated water tank 42 can be adjusted appropriately according to the purpose by adjusting the opening of the valves 47 and 48. Although not shown, it is advisable to feed back the flow values of the flow meters 86 and 87 while adjusting the opening of the valves 47 and 48 to adjust to the desired flow value. It is preferable to increase the amount of water supplied to the RO membrane 21F than the minimum amount of concentrated water of the RO membrane 21F by returning a part of the concentrated water to the tank 31 in this way. At this time, although the developing waste liquid is heated by the liquid conveying device 33, it is cooled by the cooler 91, so the concentrated water returned to the liquid tank 31 is preferably at room temperature, for example. Generally, in the development step of the resist film, since the heating of the developer solution or the heating of the pure water of the cleaning solution is not performed, the development waste liquid is at room temperature. However, because the concentrated water returned to the liquid tank 31 is cooled, even if the concentrated water returns to the liquid tank 31, the liquid temperature in the liquid tank 31 can be prevented from being too high.

The mass balance shown in FIG. 2 illustrates, for example, a specific example of the processing method of the developing waste liquid. The following numerical values of flow rate, mass %, pH, etc. are examples and are not limited to these values. The developing waste liquid system, for example, has a TMAH concentration of 0.476% by mass, a pH of 12 or more, a resist concentration (absorbance at a wavelength of 290nm, optical path length of 10mm) of 0.660 and a flow rate of 200L/h supplied to the tank 31 as supply water ( RO raw water). Hereinafter, the resist concentration is referred to as absorbance at a wavelength of 290 nm. In addition, a part of the concentrated water (circulated water) of the developing waste liquid obtained by the RO membrane device 21 is mixed with 520 L/h in the above-mentioned developing waste liquid, so that the amount of water supplied to the RO membrane device 21 is 720 L/h. Thereby, the concentrated water of the RO membrane device 21 can be made into 600L/h which is a concentrated water volume (for example, 600L/h) or more, and the permeated water can be made into 120L/h.

For example, the TMAH concentration of the water supplied to the RO membrane device 21 is 0.988% by mass, the pH is 12 or higher, and the resist concentration is 1.347. In addition, the TMAH concentration of the concentrated water of the RO membrane device 21 is 1.185 mass %, the pH is 12 or higher, and the resist concentration is 1.518. The TMAH concentration of the permeated water of the RO membrane device 21 is 0.003% by mass, the pH is 10.4 or higher, and the resist concentration is 0.000. The above-mentioned concentrated water is not completely returned to the liquid tank 31, for example, 520 L/h is returned, and the remaining 80 L/h is sent to the concentrated water tank 42 as the discharged water of the concentrated water. Collect the pH, TMAH concentration, and resist concentration in the above example, as shown in Table 1.

[Table 1]

In this way, 200 L/h of developing waste liquid is constantly supplied, and then 120 L/h is discharged as permeated water and 80 L/h is discharged as concentrated water, thereby returning the remaining concentrated water 520 L/h to the liquid tank 31. Since the concentrated water (concentrated discharge water: discharge side) sent to the concentrated water tank 42 is 80L/h with respect to the [developing waste] 200L/h, it becomes the operating condition of 200/80=2.5 times concentration (resist concentration also becomes Roughly 2.5 times concentrated). In the above situation, in order to achieve the goal of 2.5 times enrichment, the mass balance described above is achieved. It is preferable to return a part of the concentrated water through the concentrated water return system 40 and maintain the flow rate of the feed water supplied to the RO membrane device 21 at the minimum concentrated water volume of 720 L/h, thereby achieving a mass balance. That is, it is better to balance the liquid amounts to ensure the amount of water required for stable operation of the RO membrane device 21 and achieve the target concentration ratio. In addition, each of the above-mentioned flow rates is an example and is not limited to the above-mentioned flow rate values.

As shown in FIG. 3, the processing time of the developing waste liquid has passed and the RO membrane is blocked by the resist, so the permeation flux decreases and the operating pressure increases. Therefore, it is better to clean the RO membrane 21F when the permeation flux and/or operating pressure reach a critical value, for example. In addition, it is preferable to perform the cleaning of the RO film 21F when, for example, a predetermined time (for example, 1200 hours) has passed for the processing time of the developing waste liquid. In addition, by cleaning, the permeation flux and operating pressure can be returned to the initial state. Therefore, it is best to clean the RO membrane 21F regularly. Although the specifications of the RO membrane 21F are different, it is best to clean the RO membrane 21F when the permeation flux reaches about 60% of the initial state (for example, 0.4 m/d or less). Or it is better to clean the RO membrane 21F when the operating pressure reaches about 1.5 times (for example, 1.8 MPa or more) of the initial state.

Next, a preferred example of the cleaning method of the RO membrane 21F of the RO membrane device 21 will be described. When cleaning the RO membrane 21F of the RO membrane device 21, the developing waste liquid in the system of the RO membrane device 21 is discharged all at once. At this time, the concentrated water after processing the developing waste liquid in the concentrated water tank 42 and the permeated water after processing the developing waste liquid in the permeated water tank 62 are also discharged. Then, including the pipes, the liquid tank 31 and the RO membrane are respectively drained The inside of the device 21, the concentrated water tank 42, and the permeated water tank 62. Next, fresh TMAH liquid is supplied to the liquid tank 31. Then the valve 68 is closed and the valve 67 is opened, so that the permeated water return system 60 is opened. Then, the valve 48 is closed and the valve 47 is opened, so that the concentrated water return system 40 is opened. In this way, the concentrated water return system 40 returning from the liquid tank 31 to the liquid tank 31 through the cleaning liquid supply system 30A, the concentration side 21C of the RO membrane device 21, the concentrated water pipe 41, and the concentrated water return pipe 46 is opened. At the same time, it is better to open the permeated water return system 60 from the liquid tank 31 through the cleaning liquid supply system 30A, the permeate side 21T of the RO membrane device 21, the permeated water pipe 61, and the permeated water return pipe 66 to the liquid tank 31. Make the full amount of cleaning liquid circulate.

Specifically, first, fresh TMAH liquid is supplied to the liquid tank 31 for removing the developing waste liquid as a cleaning liquid. The supply amount is preferably more than the minimum concentrated water amount of the RO membrane 21F. For the new TMAH solution, a general TMAH developer with a TMAH concentration of 2.38% by mass that is not used for resist film development can be used, or a TMAH developer with a higher concentration than general TMAH developer can be used. The TMAH concentration of the cleaning solution can be changed appropriately. The new TMAH liquid is delivered to the RO membrane device 21 by the liquid delivery device 33, and then the water supply side of the RO membrane 21F is cleaned. In this case, in order not to wastefully use the TMAH fresh liquid and to ensure the minimum amount of concentrated water of the RO membrane 21F, it is better to return the cleaning liquid that has passed through the RO membrane device 21 to the liquid tank 31. At the same time, it is preferable that the concentrated water discharged from the concentration side 21C is returned to the liquid tank 31 in full. Thereby, it is better to ensure that the amount of liquid supplied to the RO membrane device 21 is greater than the minimum concentrated water amount of the RO membrane 21F.

An example of the above cleaning time is preferably 4 hours. For example, after 50L of TMAH fresh liquid is supplied to the liquid tank 31, the concentrated water return system 40 and the permeated water return system 60 are used to circulate it back to the liquid tank 31. At this time, circulate the cleaning solution to ensure the minimum amount of concentrated water. Then, the cleaning liquid is circulated in the same manner. It is best to repeat this step for 4 hours. After 4 hours of cleaning by the cleaning method described in Figure 1 above, the results of the TMAH concentration of the cleaning solution and the resist concentration of the cleaning solution as the water supply to the RO membrane device 21 with respect to the cleaning time are shown in Table 2 and Figure 4 in. As shown in Table 2 and FIG. 4, as the cleaning liquid, a TMAH concentration of, for example, 2.50% by mass is used as a new TMAH liquid. For example, after .025 hours from the start of cleaning, the developing waste liquid with a small TMAH concentration remaining in the system is mixed to reduce the TMAH concentration. Generally, the TMAH concentration of the developer is 2.38% by mass, so the TMAH concentration of the cleaning solution decreases. Later, the TMAH concentration was generally stable.

The flow rate of the cleaning liquid before the RO membrane device 21 (measured by a flow meter (not shown)) is preferably greater than the minimum concentrated water volume of the RO membrane 21F. For example, the above-mentioned concentrated water is not sent to the concentrated water tank 42 as the drain water of the concentrated water, but the entire amount is returned to the liquid tank 31. For example, let 600L/h return as concentrated water circulating water. In addition, it is preferable that the permeated water is also returned to the tank 31 in full (to be fully circulated). In this way, even if both concentrated water and permeated water are circulated in full, since the minimum concentrated water volume of the RO membrane 21F is ensured, there is no need to worry about high concentration in the RO membrane 21F.

In addition, the concentration of the resist in the cleaning solution collected and measured by the permeated water collection pipe 34 in front of the RO membrane device 21 is 0 at the beginning and increases as the cleaning is performed, but as shown in Table 2 and Figure 4 Ground, the concentration rise almost stopped after 3 to 4 hours from the start of cleaning. The fact that the resist concentration does not substantially increase means that the resist is hardly removed by cleaning. In other words, it means that there is no resist removed by cleaning. That is, it indicates that the cleaning is completed. Therefore, the cleaning time is preferably 4 hours, for example. Although the cleaning time varies with the TMAH concentration of the cleaning liquid, the flow rate of the cleaning liquid, etc., it can be said that a sufficient cleaning effect can be obtained if it is carried out for 4 hours.

[Table 2]

Because the above-mentioned cleaning is done with new TMAH solution, there is no need to clean with pure water after removing the developer used for cleaning. The waste developer can be treated immediately after the cleaning step. For example, as shown in Table 3, it takes 0.25 hours to remove the developing waste liquid, 0.25 hours to input the cleaning solution, 4 hours to clean, and 0.25 hours to remove the cleaning solution, which only requires 4.75 hours of cleaning time in total. On the other hand, the cleaning solution can use a strong alkali sodium hydroxide solution, but in this case, for example, as shown in Table 3, it is necessary to perform pure water cleaning for about 10 hours after cleaning, so that the system does not Residual sodium. For example, it takes 0.25 hours to remove developing waste liquid, 0.25 hours to input cleaning solution, 4 hours to cleaning, 0.25 hour to remove cleaning solution, 0.25 hour to input pure water, 10 hours to clean the system with pure water, and pure water cleaning solution to remove It takes 0.25 hours for a total of 15.25 hours of cleaning time.

[table 3]

The above-mentioned pure water cleaning requires that the sodium concentration be as close as possible to 0% by mass, for example, 0.005% by mass or less. Therefore, as shown in Table 4 and Figure 5, at least about 10 hours of pure water cleaning is required. Even if there is only a very small amount of sodium ions, for example, leakage current will be generated when the MOS transistor is present in the gate oxide film, thereby deteriorating the switching characteristics of the transistor. Sometimes, the current flows constantly between the source and drain, and it cannot function as a transistor. In this way, sodium ions degrade the performance of the semiconductor device, so it is generally necessary not to return it to the semiconductor device step and be removed from the cleaning system.

[Table 4]

When the cleaning using the cleaning system 100A shown in FIG. 1 is performed, the TMAH fresh liquid (resist concentration 0.000) is used as the cleaning liquid, so the resist concentration of the cleaning liquid is not as high as that of the developing waste liquid. Since the cleaning liquid needs additional liquid when the cleaning liquid permeated water is discharged, the RO membrane permeated water and concentrated water of the cleaning liquid are also returned to the tank for reuse. Thereby, the cleaning flow rate of the RO membrane 21F can be ensured. In addition, because the cleaning liquid concentrated water is the concentrated water after the TMAH fresh liquid is passed through the reverse osmosis membrane device, the resist concentration is lower than the concentrated water discharged during the processing of the developing waste liquid. Therefore, even if TMAH fresh liquid, cleaning liquid permeated water and cleaning liquid concentrated water are added to the cleaning liquid with the cleaning liquid concentrated water, the resist concentration is lower than the RO concentrated water during operation and is about 1.1. The concentrated side surface of the film 21F has the ability to sufficiently remove the resist. Hereinafter, the concentrated water discharged from the concentration side 21C after the cleaning liquid passes through the RO membrane device 21 is called cleaning liquid concentrated water.

In addition, when the concentrated water of the fresh TMAH liquid produced by the RO membrane device 21 is not returned to the liquid tank 31, in order to ensure the amount of cleaning liquid, the supply amount of the fresh TMAH liquid must be large. In addition, during cleaning, when the cleaning solution concentrated water produced by the concentration side 21C of the RO membrane device 21 is supplied to the concentrated water tank 42, the concentration of concentrated water produced by processing the developing waste liquid stored in the concentrated water tank 42 becomes smaller. Therefore, it is preferable to return the entire amount of the cleaning liquid concentrated water to the liquid tank 31. Therefore, it is better to ensure the water supply amount of the cleaning solution to the RO membrane device 21 in such a way that the amount of concentrated water can be discharged to more than the minimum concentrated water amount of the RO membrane 21F.

In this way, according to the present invention, a processing system for developing waste liquid is provided, which is a processing system for developing waste liquid containing TAAH generated in the photolithography step, and also uses a part of the system composed of a reverse osmosis membrane device as a function To clean the reverse osmosis membrane device with the reverse osmosis membrane cleaning system. In Embodiment 1, the processing system has: (a-1) Liquid tank, used to store the developing waste liquid produced in the photolithography step; (b-1) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-1) A reverse osmosis membrane device, which is connected to the other end of the liquid supply pipe and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (d-1) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device; (e-1) Concentrated water return pipe, which is connected to the concentrated water pipe and supplies the concentrated water of the reverse osmosis membrane device to the liquid tank; (f-1) Permeate water piping, one end of which is connected to the permeation side of the reverse osmosis membrane device; (g-1) Thin TAAH drainage treatment equipment, connected to the other end of the permeated water pipe; and (h-1) The permeated water return pipe is connected to the permeated water pipe and supplies the permeated water of the reverse osmosis membrane device to the liquid tank, The cleaning system is to supply the TAAH fresh liquid to the liquid tank, and make the TAAH fresh liquid in the circulation system formed by the above (a-1) to (d-1) and (e-1) and the above (a-1) ) To (c-1), (f-1) and (h-1) to form a two-circulation system to circulate in a two-circulation system, thereby cleaning the system of the reverse osmosis membrane of the reverse osmosis membrane device.

Next, a description will be made with reference to a preferred embodiment (Embodiment 2) of the processing system 1 (1B) of the developing waste liquid as a processing system of the TAAH containing liquid with the cleaning system 100 (100B). As shown in FIG. 6, in addition to changing the branch position of the permeated water return pipe 66 and the arrangement of valves 67 and 68 in the above-mentioned development waste liquid treatment system 1A, the development waste liquid treatment system 1B has the same treatment as the development waste liquid The same structure of system 1 (1A). That is, the permeated water return system 60 is branched by the permeated water conveying device 63 of the permeated water pipe 61 arranged on the downstream side of the permeated water tank 62 and supplies the permeated water to the liquid tank 31. On the other side of the permeated water conveying device 63, a permeated water pipe 61 is connected to a thin TAAH drainage treatment facility 93. The permeated water return pipe 69 preferably has a valve 70 on the downstream side of the permeated water conveying device 63. In addition, it is preferable to have a valve 71 in the permeated water pipe 61 on the downstream side of the permeated water conveying device 63. When processing the developing waste liquid, the valve 71 is opened and the valve 70 is closed. On the other hand, during cleaning, on the contrary, the valve 70 is opened and the valve 71 is closed. In this way, the permeated water return system 60 (60B) that returns to the liquid tank 31 from the liquid tank 31 through the cleaning liquid supply system 30B, the permeate side 21T of the RO membrane device 21, the permeated water pipe 61, the permeated water tank 62, and the permeated water return pipe 69 is constructed. (Circulation system through side). In addition, the concentrated water circulation system is the same as in the first embodiment described above. In addition, the processing of the development waste liquid is the same as the processing system 1A of the development waste liquid.

In the above-mentioned cleaning system 100B, TMAH fresh liquid is used as the cleaning liquid. In addition, the permeated water that permeates the RO membrane device 21 stored in the permeated water tank 62 during cleaning is also used. Therefore, the resist concentration of the cleaning solution is, for example, 0.002 and the resist concentration is very low. Since the permeated water of the cleaning liquid is stored in the permeated water tank 62 in this way, when the cleaning liquid is insufficient, by supplying more than the permeated water to the liquid tank 31, the minimum concentrated water volume of the RO membrane device 21 can be secured. In addition, because the cleaning liquid only contains TMAH fresh liquid and the cleaning liquid permeate water cannot ensure a sufficient flow rate, the concentrated water after the RO membrane treatment of the cleaning liquid is also returned to the tank 31 for reuse. Thereby, the full amount of the fresh TMAH liquid supplied to the liquid tank 31 can be used efficiently, and therefore the minimum amount of concentrated water (washing liquid amount) of the RO membrane 21F can be ensured. In addition, because the concentrated water is the concentrated water of the cleaning liquid after the cleaning liquid is passed into the RO membrane device 21, the resist concentration is particularly low compared to the concentrated water discharged during the processing of the developing waste liquid. Furthermore, although the new TMAH solution and the permeated water of the cleaning solution are added together to form the cleaning solution, the resist is contained, but the concentration of the resist is particularly low compared to the development waste solution. Therefore, it has the ability to sufficiently remove the resist from the surface of the RO film 21F (the water supply side 21S). Hereinafter, the permeated water in which the cleaning liquid is passed through the RO membrane device 21 and discharged from the permeate side 21T is referred to as cleaning liquid permeated water.

As described above, when the concentrated water is not provided in the cleaning system 100B and returned to the system 40B, in order to ensure the amount of cleaning liquid, it is necessary to increase the supply amount of permeated water from the permeate tank 62 or increase the supply amount of TMAH fresh liquid. In addition, when the cleaning solution concentrated water produced by the concentration side 21C is supplied to the concentrated water tank 42, the concentration of the concentrated water stored in the concentrated water tank 42 is small. Therefore, it is better to return the full amount of concentrated water to the tank 31 during cleaning. Therefore, it is better to ensure the water supply amount of the cleaning solution to the RO membrane device 21 in such a way that the amount of concentrated water can be discharged to more than the minimum concentrated water amount of the RO membrane 21F.

Because the above-mentioned cleaning uses the permeated water after the RO membrane device is used to process the new TMAH solution and the developing waste liquid, there is no need to perform pure water washing after the washing, and the developing waste liquid can be treated immediately after the washing step.

As described above, in the second embodiment of the processing system for the development waste liquid as the TAAH-containing liquid processing system of the present invention, the processing system for the development waste liquid has: (a-2) Liquid tank, used to store the developing waste liquid produced in the photolithography step; (b-2) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-2) A reverse osmosis membrane device connected to the other end of the liquid supply pipe; (d-2) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-2) Concentrated water return pipe, which is connected to the concentrated water pipe and supplies the concentrated water of the reverse osmosis membrane device to the liquid tank; (f-2) Permeate water piping, one end of which is connected to the permeation side of the reverse osmosis membrane device; (g-2) The permeated water tank is arranged in the middle of the permeated water pipe; (h-2) Thin TAAH drainage treatment equipment, connected to the other end of the permeate pipe; and (i-2) The permeated water return pipe is connected to the permeated water pipe located between the permeated water tank and the thin TAAH drainage treatment facility and supplies the permeated water of the reverse osmosis membrane device to the liquid tank, The cleaning system is to supply TAAH fresh liquid to the liquid tank, and make the TAAH fresh liquid in the circulation system formed by the above (a-2) to (d-2) and (e-2) and the above (a-2) ) To (c-2), (f-2), (g-2) and (i-2) to form a two-circulation system, thereby cleaning the reverse osmosis membrane of the reverse osmosis membrane device system.

Next, a description will be made with reference to a preferred embodiment (Embodiment 3) of the processing system 1 (1C) of the developing waste liquid as a processing system of the TAAH containing liquid with the cleaning system 100 (100C). As shown in FIG. 7, the processing system 1C for the development waste liquid is mainly a structure that combines the aforementioned processing systems 1A and 1B for the development waste liquid. That is, another permeated water return pipe 69 is arranged, and this permeated water return pipe 69 is connected to the permeated water tank 62 arranged in the permeated water pipe 61. Disposed in the other permeated water return pipe 69: another RO membrane device 72 which concentrates the permeated water in the permeated water tank 62; and the permeated water concentration tank 73 which temporarily stores the concentrated water of the other RO membrane device 72. The other permeated water return pipe 69 is connected to the permeated water concentration tank 73 from the concentration side 72C of the other RO membrane device 72. The other permeated water return pipe 69 may be directly connected to the permeated water concentrated water tank 73, or may be connected to the permeated water return pipe 66 on the upstream side of the permeated water concentrated water tank 73 as shown in the figure. The permeated water return pipe 66 is preferably the same as the permeated water return pipe 66 of the aforementioned developing waste liquid processing system 1A. Preferably, the permeated water concentrated water tank 73 is arranged in the permeated water return pipe 66 and the permeated water conveying device 75 is further arranged on the liquid tank 31 side. The other permeated water pipe 74 is preferably connected to the thin TAAH drainage treatment equipment 93 on the permeate side 72T of the RO membrane device 72. The permeated water return pipe 66 preferably has a valve 67 on the downstream side of the branch from the permeated water return pipe 66. In addition, it is preferable to have a valve 68 in the permeated water pipe 61 on the downstream side branching from the permeated water return pipe 66. When processing the developing waste liquid, the valve 68 is opened and the valve 67 is closed. In addition, the valve 71 is opened and the valve 70 is closed. On the other hand, when cleaning, the valve 67 is opened and the valve 68 is closed instead. In this way, a permeated water return system 60C is constructed by which the liquid tank 31 passes through the cleaning liquid supply system 30C, the permeate side 21T of the RO membrane device 21, the permeated water pipe 61, the permeated water return pipe 66, and the permeated water concentrated water tank 73 return to the liquid tank 31 ( Circulatory system on the penetrating side). The other structure is the same as the processing system 1A, 1B of the developing waste liquid. In addition, the processing of the development waste liquid is the same as the processing system 1A of the development waste liquid.

In the above-mentioned cleaning system 100C, the RO membrane permeated water of the developing waste liquid stored in the permeated water tank 62 is used as the cleaning liquid. Therefore, the resist concentration of the cleaning solution is, for example, 0.027 and the resist concentration is very low. Furthermore, since the other RO membrane device 72 passes through, the water permeates through the permeation side 72T and the TMAH concentration increases on the concentration side 72C. Therefore, concentrated water with increased TMAH concentration can be obtained. In addition, it is preferable to store the permeated water of the cleaning liquid passing through the RO membrane device 21 in the permeated water tank 62 and reuse it as a cleaning liquid during cleaning. However, since only the permeated water of the cleaning liquid cannot ensure a sufficient flow rate during cleaning, it is preferable that the concentrated water after the RO membrane treatment of the cleaning liquid is also returned to the tank 31 as the cleaning liquid for reuse. Thereby, the minimum amount of concentrated water (cleaning flow rate) of the RO membrane 21F can be ensured.

In addition, because the cleaning liquid concentrated water is the concentrated water after the cleaning liquid is passed into the RO membrane device 21, the resist concentration is particularly low compared to the concentrated water discharged during the processing of the developing waste liquid. Moreover, although the concentrated water of the cleaning liquid and the permeated water of the cleaning liquid are added together to form the cleaning liquid, it contains resist, but compared with the development waste liquid, the resist concentration is particularly low, so it has the surface of the RO film 21F ( The concentrated side 21C of the RO membrane 21F) has the ability to fully remove the resist.

As described above, when the concentrated water return system 40C is not provided in the washing system 100C, in order to ensure the amount of washing liquid, the supply amount of permeated water from the permeated water tank 62 must be increased. In addition, when the concentrated water of the cleaning solution generated by the concentration side 21C is supplied to the concentrated water tank 42, the concentration of concentrated water stored in the concentrated water tank 42 is lower than the concentration of concentrated water obtained by processing the developing waste liquid. Therefore, it is better to return the full amount of concentrated water to the tank 31 during cleaning. Therefore, it is better to ensure the water supply amount of the cleaning solution to the RO membrane device 21 in such a way that the amount of concentrated water can be discharged to more than the minimum concentrated water amount of the RO membrane 21F.

Because the above-mentioned cleaning uses the permeated water cleaning after the development waste liquid is processed by the RO membrane device, there is no need to remove the cleaning liquid in the processing system 1C of the development waste liquid and then perform the pure water cleaning, and the development can be performed immediately after the cleaning step Disposal of waste liquid.

As described above, in the third embodiment of the processing system for the development waste liquid as the TAAH-containing liquid processing system of the present invention, the processing system for the development waste liquid has: (a-3) Liquid tank, used to store the developing waste liquid produced in the photolithography step; (b-3) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-3) Reverse osmosis membrane device (Y), connected to the other end of the liquid supply pipe; (d-3) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-3) Concentrated water return piping, connected to the concentrated water piping and supplying the concentrated water of the reverse osmosis membrane device (Y) to the liquid tank; (f-3) Permeate water pipe (P), one end of which is connected to the permeate side of the reverse osmosis membrane device (Y); (g-3) The permeated water tank is arranged in the middle of the permeated water pipe (P); (h-3) Thin TAAH drainage treatment equipment, connected to the other end of the permeate pipe (P); (i-3) The permeated water return pipe (I) is connected to the permeated water pipe (P) between the reverse osmosis membrane device (Y) and the permeated water tank and supplies the reverse osmosis membrane device (Y) Permeate water to the above liquid tank; (j-3) The permeated water concentration tank is arranged in the middle of the permeated water return pipe (I); (k-3) Another permeated water return pipe (II), which is branched from the permeated water pipe (P) between the permeated water tank and the thin TAAH drainage treatment facility, and is connected to the reverse osmosis membrane The permeated water return pipe (I) between the device (Y) and the permeated water concentration tank; (l-3) Another reverse osmosis membrane device (Z) is arranged in the middle of the other permeated water return pipe (II); and (m-3) Another permeated water pipe (Q), which connects the permeate side of the other reverse osmosis membrane device (Z) and the above-mentioned thin TAAH drainage treatment equipment, The cleaning system is to supply concentrated water (X) that concentrates the permeated water of the reverse osmosis membrane device (Y) by the other reverse osmosis membrane device (Z) to the liquid tank, and make the concentrated water (X) The circulatory system formed by the above (a-3) to (d-3) and (e-3) and the above (a-3) to (c-3), (f-3), (i-3) and ( j-3) A system that circulates in the two-circulation system of the formed circulation system, thereby cleaning the reverse osmosis membrane of the above-mentioned reverse osmosis membrane device.

Next, a description will be made with reference to a preferred embodiment (Embodiment 4) of the processing system 1 (1D) of the developing waste liquid as a processing system of the TAAH containing liquid with the cleaning system 100 (100D). As shown in Fig. 8, the processing system 1D of the development waste liquid is in the same concentrated water return system 40D as the concentrated water return system 40A of the aforementioned processing system 1A of the development waste liquid, and the concentrated water of the concentrated water tank 42 is combined to be concentrated. The structure of the concentrated water permeation system 50 of the water return pipe 46. That is, it is preferable that the concentrated water permeation piping 51 of the concentrated water permeation system 50 is branched by the concentrated water piping 41 between the concentrated water transfer device 43 and the evaporator 11 and connected to the concentrated water return piping 46 between the cooler 91 and the flow meter 87 . It is preferable to arrange a nanofiltration (NF) device 52, an NF permeation tank 53, and an NF permeate transfer device 54 in the concentrated water permeation pipe 51 from the branch side of the concentrated water pipe 41 in this order. In addition, it is preferable that the concentrated water permeation pipe 51 is connected to the permeation side 52T of the NF device 52 and the concentrated water pipe 55 connected to the evaporator 11 is connected to the concentration side 52C of the NF device 52. Preferably, the concentrated water permeation pipe 51 is provided with a valve 56 on the branch side from the concentrated water pipe 41 and the concentrated water pipe 41 is provided with a valve 57 on the evaporator 11 side from the branch point of the concentrated water permeable pipe 51. In this way, a concentrated water return system 40D (concentrated water circulation system) in which the liquid tank 31 returns to the liquid tank 31 through the cleaning liquid supply system 30D, the concentration side 21C of the RO membrane device 21, the concentrated water pipe 41 and the concentrated water return pipe 46 is constructed. The other structure is the same as the processing system 1A for developing waste liquid. In addition, the processing of the development waste liquid is the same as the processing system 1A of the development waste liquid.

When cleaning by the above-mentioned cleaning system 100D, similar to the cleaning system 100A, it is preferable to remove all the liquid in the cleaning system 100D first, and then supply the new TMAH liquid to the liquid tank 31 as the cleaning liquid. When cleaning, open valve 47 and valve 48 on the concentration side. Then adjust the opening amount appropriately. At the same time, valve 57 is closed and valve 56 is opened. At the same time, the valve 68 on the permeate side is closed and the valve 67 is opened. Since the cleaning system 100D uses a fresh TMAH solution as a cleaning solution, the TMAH concentration is high (for example, 2.38% by mass), and therefore the RO film 21F has excellent resist cleaning properties. However, only the TMAH fresh liquid as the cleaning liquid has an insufficient flow rate, so the cleaning liquid permeated water discharged from the RO membrane device 21 is used and the cleaning liquid concentrated water discharged from the RO membrane device 21 is also used. Although a part of the cleaning liquid concentrated water is returned to the liquid tank 31 by the concentrated water return system 40D, the remaining part is stored in the concentrated water tank 42. The cleaning liquid concentrated water stored in the concentrated water tank 42 is passed to the NF device 52. The resist is removed in the NF device 52 and the TMAH aqueous solution is permeated, and then the concentrated water is supplied to the concentrated water return pipe 46 from the concentrated water permeation pipe 51 and sent to the liquid tank 31. Therefore, a solution having a low resist concentration (for example, a resist concentration of 0.012) and increasing the TMAH concentration by the RO film device 21 (for example, a TMAH concentration of 2.21% by mass) is supplied to the liquid tank 31. Therefore, even if a part of the cleaning liquid concentrated water is directly supplied to the liquid tank 31, the resist concentration is small and the TMAH concentration is high. In the above system, because TMAH is hardly removed and the resist is removed by the NF device 52, the resist concentration is low (for example, 1/99) compared to the case where the full amount of the cleaning solution concentrated water is returned to the tank 31 the following). In this way, only the permeated water of the cleaning liquid cannot ensure a sufficient flow rate. Therefore, the concentrated water of the cleaning liquid after the RO membrane processes the cleaning liquid is also returned to the liquid tank 31 as the cleaning liquid for reuse. Thereby, the minimum amount of concentrated water (cleaning flow rate) of the RO membrane 21F can be ensured. In addition, because the cleaning liquid concentrated water system is the concentrated water after the TMAH fresh liquid is passed through the RO membrane device 21, the resist concentration is lower than the concentrated water discharged during the processing of the developing waste liquid. Therefore, the concentration of the resist in the cleaning solution combined with the permeated water and concentrated water is very low, so it has the ability to remove the resist from the concentrated side surface of the RO membrane 21F.

Because the above-mentioned cleaning is cleaning with new TMAH solution, there is no need to perform pure water cleaning after removing the cleaning solution in the processing system 1D of the development waste liquid. The development waste liquid can be treated immediately after the cleaning step.

As described above, in the fourth embodiment of the processing system for the development waste liquid as the processing system for the TAAH-containing liquid of the present invention, the processing system for the development waste liquid has: (a-4) Liquid tank, used to store the developing waste liquid produced in the photolithography step; (b-4) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-4) A reverse osmosis membrane device connected to the other end of the liquid supply pipe; (d-4) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device; (e-4) The concentrated water tank is arranged in the middle of the concentrated water piping; (f-4) The concentrated water return pipe is connected to the concentrated water pipe located between the reverse osmosis membrane device and the concentrated water tank and supplies the concentrated water of the reverse osmosis membrane device to the liquid tank; (g-4) Concentrated water permeation piping, which is branched from the concentrated water piping located between the concentrated water tank and the evaporator and connected to the concentrated water return piping; (h-4) The nanofiltration device is arranged in the middle of the concentrated water permeation pipe; (i-4) A nanofiltration permeable water tank is arranged in the middle of the concentrated water permeation piping and stores the permeated water of the above-mentioned nanofiltration device; (j-4) A nanofiltration concentrated water pipe, one end of which is connected to the concentration side of the nanofiltration device and supplies the concentrated water of the nanofiltration device to the evaporator; (k-4) Permeate water piping, one end of which is connected to the permeation side of the reverse osmosis membrane device; (l-4) Thin TAAH drainage treatment equipment, connected to the other end of the permeate pipe; and (m-4) The permeated water return pipe is connected to the permeated water pipe and supplies the permeated water to the liquid tank, The cleaning system is to supply new TMAH liquid to the liquid tank, and make the new TMAH liquid in the circulation system formed by the above (a-4) to (e-4) and (f-4) to (i-4) and Circulate in the two-circulation system of the circulation system formed by the aforementioned (a-4) to (c-4), (k-4) and (m-4), thereby cleaning the reverse osmosis membrane of the above-mentioned reverse osmosis membrane device system.

Next, a description will be made with reference to a preferred embodiment (Embodiment 5) of the processing system 1 (1E) of the developing waste liquid as a processing system of the TAAH containing liquid with the cleaning system 100 (100E). As shown in Figure 9, the processing system 1E for the development waste liquid is in the aforementioned processing system 1C for the development waste liquid. The permeated water return pipe 69 between the permeated water conveying device 63 and the permeated water concentration tank 73 Another RO membrane device 72 and an NF device 76 are arranged in sequence on the side of the water conveying device 63. Preferably, another permeated water return pipe 69 for supplying permeated water in the permeate tank 62 is connected to the feed water side 72S of the other RO membrane device 72, and the other permeated water return pipe 69 is connected to the above by the concentration side 72C of the RO membrane device 72 The water supply side 76S of the NF device 76. Preferably, another permeated water pipe 74 is connected to the thin TAAH drainage treatment facility 93 on the permeate side 72T of the other RO membrane device 72. In addition, it is preferable that another permeated water return pipe 69 is connected to the permeated water concentration tank 73 from the permeate side 76T of the NF device 76. The concentration side 76C of the NF device 76 is preferably connected to another permeated water pipe 74 through another concentrated water pipe 77. As shown in the figure, another permeated water return pipe 69 may be connected to the permeated water concentration tank 73 through the permeated water return pipe 66. In this way, a permeated water return system 60E in which the liquid tank 31 passes through the processed liquid supply system 30E, the permeate side 21T of the RO membrane device 21, the permeated water pipe 61, the permeated water return pipe 66, and the permeated water concentration tank 73 return to the liquid tank 31 is constituted. (Circulation system on the enrichment side). The other structure is the same as the processing system 1C for developing waste liquid. In order to use the processing system 1E for the waste development liquid to treat the waste development liquid, it is preferable to perform the valve operation in the same manner as the processing system 1A for the waste development liquid. In addition, during cleaning, in order to transport the permeated water from the permeated water tank 62 storing the permeated water of the developing waste liquid to the liquid tank 31, it is preferable to close the valve 71 and open the valve 70. Then, after the permeated water of the NF device 76 is stored in the permeated water concentration tank 73, the valve 68 is closed and the valve 67 is opened.

In the above-mentioned cleaning system 100E, it is preferable that the permeated water of the developing waste liquid stored in the permeated water tank 62 passes through another RO membrane device 72 and the concentrated water is further passed into the NF device 76, and then the permeated water is used as the cleaning liquid . Therefore, since the permeated water of the developing waste liquid is discharged to the permeate side by the RO membrane device 72 and TMAH remains on the concentration side, the TMAH concentration increases. In addition, because the liquid with increased TMAH concentration passes through the NF device 76, the TMAH penetrates and removes the resist. Therefore, a cleaning solution that is a solution in which the TMAH concentration is increased and the resist is decreased is supplied to the permeated water concentration tank 73. The resist concentration of the cleaning solution is, for example, 0.001 and the resist concentration is very low. In addition, by concentrating the TMAH concentration by another RO membrane device 72, the TMAH concentration can be suppressed from being too low. Since only the permeated water of the developing waste liquid cannot ensure a sufficient flow rate of the cleaning liquid, it is better to return the concentrated water of the cleaning liquid after the RO membrane treatment of the cleaning liquid to the liquid tank 31 as the cleaning liquid for reuse. Thereby, the minimum amount of concentrated water (cleaning flow rate) of the RO membrane 21F can be ensured. In addition, because the concentrated water-based cleaning liquid of the cleaning liquid is passed into the concentrated water after the RO membrane device 21, the resist concentration is lower than the concentrated water discharged during the processing of the developing waste liquid. Moreover, although the concentrated water of the cleaning solution and the permeated water of the cleaning solution are added together to form a cleaning solution, it contains a resist, but the concentration of the resist is particularly low compared to the development waste liquid, so it can be sufficiently removed from the reverse osmosis membrane surface. The ability of resist.

As described above, when the concentrated water return system 40E is not provided in the washing system 100E, in order to ensure the amount of washing liquid, the supply amount of permeated water from the permeated water tank 62 must be increased. In addition, when the concentrated water of the cleaning solution generated from the concentration side 21C is supplied to the concentrated water tank 42, the concentration of the concentrated water stored in the concentrated water tank 42 is small when the developing waste liquid after washing is processed. Therefore, it is better to return the full amount of concentrated water to the tank 31 during cleaning. Therefore, it is better to ensure the water supply amount of the cleaning solution to the RO membrane device 21 in such a way that the amount of concentrated water can be discharged to more than the minimum concentrated water amount of the RO membrane 21F.

Because the above-mentioned cleaning uses the permeated water cleaning after the development waste liquid is processed by the RO membrane device, there is no need to perform pure water cleaning after removing the cleaning liquid in the processing system 1E for the development waste liquid. It can be performed immediately after the cleaning step Disposal of developing waste liquid.

As described above, in the fifth embodiment of the processing system for the development waste liquid as the TAAH-containing liquid processing system of the present invention, the processing system for the development waste liquid has: (a-5) Liquid tank, used to store the developing waste liquid produced in the photolithography step; (b-5) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-5) Reverse osmosis membrane device (Y), connected to the other end of the liquid supply pipe; (d-5) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-5) Concentrated water return piping, connected to the concentrated water piping and supplying the concentrated water of the reverse osmosis membrane device (Y) to the liquid tank; (f-5) Permeate water pipe (P), one end of which is connected to the permeation side of the reverse osmosis membrane device (Y); (g-5) Permeated water tank, arranged in the middle of the permeated water pipe (P); (h-5) Thin TAAH drainage treatment equipment, arranged at the other end of the permeated water pipe (P); (i-5) The permeated water return pipe (I) is connected to the permeated water pipe (P) between the reverse osmosis membrane device (Y) and the permeated water tank and supplies the reverse osmosis membrane device (Y) Permeate water to the above liquid tank; (j-5) The permeated water concentration tank is arranged in the middle of the permeated water return pipe (I); (k-5) Another permeated water return pipe (II), which is branched from the permeated water pipe (P) between the permeated water tank and the thin TAAH drainage treatment facility, and is connected to the reverse osmosis membrane The permeated water return pipe (I) between the device (Y) and the permeated water concentration tank; (l-5) Another reverse osmosis membrane device (Z) is arranged in the middle of the other permeated water return pipe (II); (m-5) The nanofiltration device is arranged in the middle of the other permeated water return pipe (II) and treats the concentrated water of the other reverse osmosis membrane device (Z); (n-5) Another permeate pipe (Q), which connects the permeate side of the other reverse osmosis membrane device (Z) and the above-mentioned thin TAAH drainage treatment equipment; and (o-5) Nanofiltration concentrated water piping, which connects the concentration side of the nanofiltration device and the other permeated water piping (Q), The cleaning system supplies the permeated water of the reverse osmosis membrane device (Y) through the other reverse osmosis membrane device (Z) to concentrate and further permeate the permeated water treatment water of the nanofiltration device to the liquid tank, and The above-mentioned permeated water treatment water is in the circulation system formed by the above (a-5) to (d-5) and (e-5) and the above (a-5) to (c-5), (f-5) and (i-5) A system that circulates in the two-circulation system of the formed circulation system, thereby cleaning the reverse osmosis membrane of the above-mentioned reverse osmosis membrane device.

In the processing systems 1B to 1E for the above-mentioned development waste liquid, when the processing of the development waste liquid is performed, the development waste liquid is supplied to the liquid tank 31 and sent to the RO through the liquid supply pipe 32 in the same manner as the processing system 1A for the above-mentioned development waste liquid.膜装置21。 Film device 21. The developing waste liquid is separated into concentrated water and permeated water by the RO membrane device 21. A part of the concentrated water returns to the system 40 through the concentrated water and is cooled by the cooler 91 and then returns to the liquid tank 31. On the other hand, the remaining part of the concentrated water passes through the concentrated water pipe 41 and is introduced into the concentrated water tank 42, and then is sent to the evaporator 11. In the treatment of the developing waste liquid, it is better to operate the valve so that the developing waste liquid does not flow into the cleaning liquid system side. For example, it is preferable to close the valve 67 in the treatment system 1A, close the valve 70 in the treatment system 1B, close the valves 67 and 70 in the treatment systems 1C and 1E, and close the valves 56 and 67 in the treatment system 1D.

Although the above-mentioned processing system 1A for developing waste liquid shows an example of mass balance, other processing systems 1B to 1E for developing waste liquid can also be used with membranes such as RO membranes, NF membranes, and the like to set mass balances appropriately.

In each of the above-mentioned processing systems 1A to 1E of the developing waste liquid, it is preferable to have a device for measuring the resist concentration of the cleaning liquid supplied from the liquid tank 31 through the cleaning systems 100A to 100E. For example, it is preferable to obtain a sample from the collection pipe 34 and to measure the resist concentration of the sample by an absorbance spectrophotometer using, for example, the aforementioned spectrophotometer. In addition, it is preferable to have a cleaning state detection device (not shown) that detects the cleaning state from the measured resist concentration. The cleaning state detection device compares the above-mentioned measured value of the resist concentration with the threshold value of the resist concentration to be cleaned to determine whether to perform the cleaning step.

The above-mentioned processing systems 1A to 1E of each developing waste liquid are preferably measured by measuring any of the treated water volume, permeated water volume, operating pressure, and pressure difference between the membranes (the difference between the pressure on the feed water side and the pressure on the permeate side) of the RO membrane device 21 Above, the membrane clogging state of the RO membrane 21F of the RO membrane device 21 is detected. The detection method is to obtain the treated water volume of the RO membrane device 21 from the total value of the flow rates measured by the flow meters 86 to 88. The amount of permeated water is measured by a flow meter 88. In addition, the operating pressure is measured by the pressure gauge 81. The pressure difference between the membranes (the difference between the pressure on the feed water side and the pressure on the permeate side) is measured by pressure gauges 81 and 83 and the pressure difference is obtained.

In the processing systems 1A to 1E of the above-mentioned developing waste liquid, it is best to judge whether the clogging state of the RO membrane 21F detected is transferred to the cleaning step of the RO membrane device 21, and to the RO membrane when it is necessary to transfer to the cleaning step Cleaning steps of the device. It is best to judge whether there is a transition to the cleaning step: when the treated water volume reaches approximately 60% by mass at the initial stage, when the permeate volume reaches approximately 60% by mass at the initial stage, when the operating pressure reaches approximately 1.8MPa, the pressure difference between the membranes reaches approximately 1.8 At least one of them at MPa is transferred to the cleaning step. Although new TMAH liquid is used as the cleaning solution in the processing systems 1A and 1B of the above-mentioned developing waste liquids, the concentrated water containing TMAH is stored in the permeated water concentrated water tank 73 in the above-mentioned processing systems 1C and 1E of the developing waste liquids. In the above-mentioned processing system 1D of each developing waste liquid, the permeated water containing TMAH is stored in the NF permeated water tank 53, and the stored liquid can be used as a cleaning liquid. Therefore, the usage amount of the new TMAH solution can be less than the above-mentioned treatment systems 1A and 1B of the respective developing waste liquids. In addition, the processing systems 1C to 1E of the developing waste liquid aim to recover the TMAH in the waste liquid as much as possible for the cleaning liquid and achieve this purpose. In addition, the new TMAH solution can of course be used in the processing systems 1C to 1E of the developing waste liquid.

Although the aforementioned RO membrane device or NF membrane device has a one-stage structure, it may also have a multi-stage structure. In this case, it is preferable that both the RO membrane and the NF membrane are arranged in multiple stages in series. Preferably, at least one of the multi-stage RO membrane devices is a high-pressure RO membrane device. Example

(Example 1) In Example 1, the processing system 1A of the waste development liquid shown in FIG. 1 was used to concentrate the waste development liquid and clean the water supply side 21S of the RO membrane 21F. The RO membrane 21F of the RO membrane device 21 uses the SWC 5 seawater desalination membrane manufactured by Nitto Denko Corporation, which is 4 inches and the membrane area is 37.1 m ² . In addition, it was confirmed that even if the RO membrane (SWC 5) was continuously operated for approximately 3620 hours (approximately 150 days) in a continuous test with a pH of 12 as described above, there was no problem in the use of the membrane including the material. The mass balance system valves 47 and 48 adjust the opening degree when the developing waste liquid is processed, and then set the same as the one shown in FIG. 2 above. Therefore, when the developing waste liquid is processed, the valves 47 and 48 are adjusted to open, and then the valve 68 is opened and the valve 67 is closed. On the other hand, during the cleaning step, valve 47 is opened and valve 48 is closed, and then valve 67 is opened and valve 68 is closed. In this state, the processing of the developing waste liquid is continued, and then a cleaning step is performed when the permeation flux is close to 0.4 m/d. Generally speaking, a 1200-hour development waste liquid treatment step is performed 3 times and a washing step is performed 2 times in between. One cleaning step is a total of 4.75 hours for the time to remove the developing waste liquid, the time to put the cleaning solution, the cleaning time, and the time to remove the cleaning solution. The developing waste liquid actually uses the developing waste liquid discharged during semiconductor manufacturing. The operating pressure is above 1.8MPa. After setting the processing conditions as described above, the development waste liquid is processed. Samples were collected from the respective collection pipes 34, 44, 64 on the supply side, concentration side, and permeation side of the RO membrane device 21, and then the test solutions (developing waste liquid, RO membrane supply water, RO membrane concentrated water, RO membrane permeation Water) pH, TMAH concentration, resist concentration (absorbance at 290nm). The results are shown in Table 1. The relationship between the elapsed time of developing waste liquid treatment and the permeation flux (m/d) is shown in FIG. 3. As the development waste liquid is processed, the permeation flux decreases. When the permeation flux is close to 0.4m/d, transfer to the cleaning step to implement RO membrane cleaning. In addition, the cleaning time can also be set arbitrarily. After the cleaning step, as shown in Fig. 3, the permeation flux and operating pressure returned to the initial state together. The initial state is the state before starting the processing of the developing waste liquid. In addition, even if the concentration treatment and cleaning steps of the developing waste liquid are repeated, the permeation flux and the operating pressure are all restored to the initial state each time the cleaning step is performed. In this way, by periodically performing the cleaning step, the processing capacity of the RO membrane 21F can be restored and the life of the RO membrane 21F can be extended. The cleaning solution uses a new TMAH developer solution with a TMAH concentration of 2.50% by mass. The new TMAH developer solution is used for the unused TMAH developer solution in the development step of photolithography. As shown in the foregoing Table 2, the TMAH concentration dropped to 2.20% by mass after the mixing of the developing waste liquid with a small TMAH concentration remaining in the system after, for example, 0.25 hours from the start of cleaning. Consider mixing permeated water with a low concentration of TMAH, for example. After the TMAH concentration decreases, it is roughly stable at the decreasing value. Because the cleaning liquid after cleaning is TMAH and water, the cleaning liquid can immediately flow into the concentrated water tank after the cleaning step.

(Comparative example 1) Except that the washing step was not performed, Comparative Example 1 was treated in the same manner as Example 1 to treat the development waste liquid. Therefore, the development waste liquid, RO membrane feed water, RO membrane concentrated water, and RO membrane permeate water pH and TMAH concentration collected from the supply side, concentration side, and permeate side of the RO membrane device 21 are collected by the pipes 34, 44, 64. And the resist concentration (absorbance at 290 nm) are the same values as in Example 1. The relationship between the elapsed time of developing waste liquid treatment and the permeation flux (m/d) is shown in FIG. 3. As the development waste liquid is processed, the permeation flux decreases. When the flux is close to 0.4m/d, the change in flux becomes smaller. When the operating pressure is close to 1.8MPa, the change in operating pressure becomes smaller. When the cleaning step is not performed in this way, the processing capacity of the RO membrane 21F cannot be restored, so the RO membrane 21F must be replaced.

(Comparative example 2) Washing was performed in the same manner as in Example 1, except that a 2.5% by mass sodium hydroxide (NaOH) aqueous solution was used. Therefore, the cleaning time is 4 hours. The flux before and after cleaning was 0.422m/d before cleaning and 0.685m/d after cleaning. In this way, even with 2.5% by mass NaOH aqueous solution cleaning, the result is the same as during TMAH cleaning. But through flux recovery, pure water cleaning is needed to remove NaOH. The pure water cleaning system is implemented until the same sodium concentration as the developing waste solution reaches 0.005% by mass or less, so that sodium ions do not affect the recovery of TMAH (please refer to the aforementioned Table 4 and Figure 5). The pure water cleaning is carried out while keeping the flow in the system. The cleaning time is 0.25 hours for developing waste liquid removal, 0.25 hours for cleaning solution input, 4 hours for cleaning, 0.25 hours for cleaning solution removal, 0.25 hours for pure water input, 10 hours for pure water cleaning in the system, pure water cleaning solution Removal takes 0.25 hours, and a total cleaning time of 15.25 hours is required (please refer to Table 3 above). As a result, it can be understood that the cleaning method using TMAH of the developing waste liquid treatment system of the present invention has fewer cleaning steps and a short cleaning time, and therefore can be cleaned efficiently and at low cost.

(Examples 2 to 5) Embodiment 2 uses the processing system 1B for the waste development liquid shown in FIG. 6 to perform the concentration treatment of waste development liquid and the cleaning steps of the RO membrane 21F. The cleaning solution uses the new TMAH developing solution as the new TMAH solution. The other conditions are the same as in Example 1. In Example 3, the processing system 1C of the developing waste liquid shown in FIG. 7 was used for the concentration treatment of the developing waste liquid and the cleaning steps of the RO membrane 21F. As the cleaning liquid, concentrated water obtained by concentrating the permeated water of the developing waste liquid passing through the RO membrane device 21 by another RO membrane device 72 is used. The other conditions are the same as in Example 1. In Example 4, the processing system 1D of the developing waste liquid shown in FIG. 8 was used for the concentration treatment of the developing waste liquid and the cleaning steps of the RO membrane 21F. The cleaning solution uses the new TMAH developing solution as the new TMAH solution. The other conditions are the same as in Example 1. In Example 5, the processing system 1E of the developing waste liquid shown in FIG. 9 was used for the concentration treatment of the developing waste liquid and the cleaning steps of the RO membrane 21F. As the cleaning liquid, the permeated water obtained by concentrating the developing waste liquid passing through the RO membrane device 21 by another RO membrane device 72 and passing the concentrated water through the NF device 76 is used. The other conditions are the same as in Example 1. The NF membrane of Examples 4 and 5 uses NF manufactured by Nitto Denko Corporation, type NTR. 7450. The cleaning results of each of Examples 1 to 5 are shown in Table 5.

As shown in Table 5, in Examples 1 to 5, the TMAH concentration of the cleaning solution was 2.20 to 2.38. Both are TMAH concentrations that can sufficiently clean the resist of the RO film 21F. In addition, the resist concentration before supplying to the RO film 21F is 0.000 to 0.027, which are all very low values. The permeation flux returns to 0.68 to 0.70 after cleaning. Regardless of the type of liquid, the recovery rate is generally restored to more than 97% and is effective for the TMAH cleaning of the developing waste liquid treatment system of the present invention.

[table 5]

Although the present invention is described together with the embodiments of the present invention, unless we specifically specify, our invention is not limited to any details of the description, but should be considered in a situation that does not violate the spirit and scope of the invention shown in the scope of the attached patent application. Explain broadly.

This application claims priority based on Japanese Patent Application No. 2018-197694 filed on October 19, 2018, and the application is referred to here and its content is added as part of the description of this specification.

1, 1A, 1B, 1C, 1D, 1E: processing system for developing waste liquid 11: Evaporator 21, 72: RO membrane device 21C, 52C, 72C, 76C: concentrated side 21F: RO membrane 21S, 72S, 76S: water supply side 21T, 52T, 72T, 76T: through side 30: Liquid supply system to be processed 30A, 30B, 30C, 30D, 30E: cleaning liquid supply system 31: Liquid tank 32: Liquid supply piping 33: Liquid delivery device 34, 64: Permeate water to take piping 35, 45, 47, 48, 56, 57, 65, 67, 68, 70, 71: Valve 40, 40A, 40B, 40C, 40D, 40E: concentrated water return system 41, 77: Concentrated water piping 42: Concentrated water tank 43: Concentrated water transfer device 44: Concentrated water take piping 46: Concentrated water return piping 50: Concentrated water permeation system 51: Concentrated water through piping 52, 76: Nanofiltration (NF) device 53: NF through the sink 54: NF permeable water transmission device 55: Concentrated water piping 60, 60A, 60B, 60C, 60D, 60E: permeated water return system 61, 74: Permeated water piping 62: Through the sink 63, 75: Water transmission device 66, 69: Permeated water return piping 73: Permeated water concentration tank 81, 82, 83: pressure gauge 86, 87, 88: Flowmeter 91: cooler 93: Thin TAAH drainage treatment equipment 100, 100A, 100B, 100C, 100D, 100E: cleaning system

[Fig. 1] is a schematic diagram showing a preferred embodiment (Embodiment 1) of a processing system for TAAH-containing liquid of the present invention. Fig. 2 is a mass balance diagram showing a preferred example of the mass balance of the TAAH-containing solution (developing waste liquid) in the TAAH-containing solution processing system of the first embodiment. [Figure 3] A graph showing the relationship between permeation flux and operating pressure and the elapsed time of TAAH-containing solution (developing waste liquid) treatment with or without a cleaning step. [Figure 4] The relationship between the TMAH concentration and the cleaning time in the cleaning step. [Figure 5] is a graph showing the relationship between Na concentration and cleaning time in the pure water cleaning step. Fig. 6 is a schematic configuration diagram showing a preferred embodiment (Embodiment 2) of a processing system for TAAH-containing liquid of the present invention. Fig. 7 is a schematic configuration diagram showing a preferred embodiment (Embodiment 3) of a processing system for TAAH-containing liquid of the present invention. Fig. 8 is a schematic configuration diagram showing a preferred embodiment (Embodiment 4) of a processing system for TAAH-containing liquid of the present invention. Fig. 9 is a schematic configuration diagram showing a preferred embodiment (Embodiment 5) of a processing system for TAAH-containing liquid of the present invention.

Claims (10)

A treatment system for tetraalkylammonium hydroxide containing liquid, comprising: a high-pressure reverse osmosis membrane device, which concentrates the treated liquid containing tetraalkylammonium hydroxide on its concentration side; and a pipeline, which is supplied to The reverse osmosis membrane device is an evaporator that further concentrates the liquid to be treated after being concentrated. For example, the tetraalkylammonium hydroxide-containing liquid treatment system of the first item in the scope of patent application has a cleaning system that cleans the reverse osmosis membrane device by a cleaning liquid containing tetraalkylammonium hydroxide. For example, the treatment system of the tetraalkylammonium hydroxide containing liquid of the first or second item of the scope of patent application can make a part of the treatment system as a circulation system composed of the reverse osmosis membrane device, and by making it contain The cleaning liquid of tetraalkylammonium hydroxide circulates in the circulation system, and the circulation system can be used as a cleaning system for cleaning the reverse osmosis membrane of the reverse osmosis membrane device. For example, the tetraalkylammonium hydroxide-containing liquid treatment system of item 3 of the scope of patent application has: (a-1) Liquid tank for storing liquid containing tetraalkylammonium hydroxide; (b-1) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-1) A reverse osmosis membrane device connected to the other end of the liquid supply pipe; (d-1) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-1) Concentrated water return piping, connected to the concentrated water piping and supplying the concentrated water of the reverse osmosis membrane device to the liquid tank; (f-1) Permeate water piping, one end of which is connected to the permeation side of the reverse osmosis membrane device; (g-1) Thin tetraalkylammonium hydroxide wastewater treatment equipment, connected to the other end of the permeate pipe; and (h-1) The permeated water return pipe is connected to the permeated water pipe and the permeated water of the reverse osmosis membrane device is supplied to the liquid tank, The cleaning system supplies the fresh tetraalkylammonium hydroxide solution to the tank, and circulates the fresh tetraalkylammonium hydroxide solution from (a-1) to (d-1) and (e-1) The formed circulation system and the two circulation systems formed by the (a-1) to (c-1), (f-1) and (h-1), while cleaning the reverse osmosis membrane device With the reverse osmosis membrane. For example, the tetraalkylammonium hydroxide-containing liquid treatment system of item 3 of the scope of patent application has: (a-2) Liquid tank for storing liquid containing tetraalkylammonium hydroxide; (b-2) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-2) A reverse osmosis membrane device connected to the other end of the liquid supply pipe; (d-2) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-2) Concentrated water return piping, connected to the concentrated water piping and supplying the concentrated water of the reverse osmosis membrane device to the liquid tank; (f-2) Permeate water piping, one end of which is connected to the permeation side of the reverse osmosis membrane device; (g-2) The permeated water tank is arranged in the middle of the permeated water pipe; (h-2) Thin tetraalkylammonium hydroxide drainage treatment equipment, connected to the other end of the permeate pipe; and (i-2) The permeated water return piping is connected to the permeated water piping located between the permeated water tank and the thin tetraalkylammonium hydroxide drainage treatment equipment, and the permeated water of the reverse osmosis membrane device is supplied to the liquid groove, The cleaning system supplies the fresh tetraalkylammonium hydroxide solution to the tank, and circulates the fresh tetraalkylammonium hydroxide solution from the (a-2) to (d-2) and (e-2) ) And the two-circulation system formed by (a-2) to (c-2), (f-2), (g-2) and (i-2), by This cleans the reverse osmosis membrane of the reverse osmosis membrane device. For example, the tetraalkylammonium hydroxide-containing liquid treatment system of item 3 of the scope of patent application has: (a-3) Liquid tank for storing liquid containing tetraalkylammonium hydroxide; (b-3) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-3) Reverse osmosis membrane device (Y), connected to the other end of the liquid supply pipe; (d-3) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-3) Concentrated water return piping, connected to the concentrated water piping and supplying the concentrated water of the reverse osmosis membrane device (Y) to the liquid tank; (f-3) Permeate water pipe (P), one end of which is connected to the permeate side of the reverse osmosis membrane device (Y); (g-3) The permeated water tank is arranged in the middle of the permeated water pipe (P); (h-3) Thin tetraalkylammonium hydroxide drainage treatment equipment, connected to the other end of the permeate pipe (P); (i-3) The permeated water return pipe (I) is connected to the permeated water pipe (P) between the reverse osmosis membrane device (Y) and the permeate tank, and the reverse osmosis membrane device (Y) Permeated water is supplied to the liquid tank; (j-3) The permeated water concentration tank is arranged in the middle of the permeated water return pipe (I); (k-3) Another permeated water return pipe (II), which is branched from the permeated water pipe (P) between the permeated water tank and the dilute tetraalkylammonium hydroxide drainage treatment equipment, and is connected in place The permeated water return pipe (I) between the reverse osmosis membrane device (Y) and the permeated water concentration tank; (l-3) Another reverse osmosis membrane device (Z) is arranged in the middle of the other permeated water return pipe (II); and (m-3) Another permeate pipe (Q), which connects the permeate side of the other reverse osmosis membrane device (Z) and the thin tetraalkylammonium hydroxide drainage treatment equipment, The cleaning system supplies concentrated water (X) obtained by condensing the permeated water of the reverse osmosis membrane device (Y) by the other reverse osmosis membrane device (Z) to the liquid tank, and makes the concentrated water (X) In the circulatory system formed by (a-3) to (d-3) and (e-3) and from (a-3) to (c-3), (f-3), (i-3) ) And (j-3) circulate in the two circulation system of the circulation system, thereby cleaning the reverse osmosis membrane of the reverse osmosis membrane device. For example, the tetraalkylammonium hydroxide-containing liquid treatment system of item 3 of the scope of patent application has: (a-4) Liquid tank for storing liquid containing tetraalkylammonium hydroxide; (b-4) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-4) A reverse osmosis membrane device connected to the other end of the liquid supply pipe; (d-4) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-4) The concentrated water tank is arranged in the middle of the concentrated water piping; (f-4) Concentrated water return piping, connected to the concentrated water piping located between the reverse osmosis membrane device and the concentrated water tank, and supply the concentrated water of the reverse osmosis membrane device to the liquid tank; (g-4) Concentrated water permeates the piping, which is branched from the concentrated water piping located on the downstream side of the concentrated water tank and connected to the concentrated water return piping; (h-4) The nanofiltration device is arranged in the middle of the concentrated water permeation pipe; (i-4) A nanofiltration permeable water tank is arranged in the middle of the concentrated water permeation pipe and stores the permeated water of the nanofiltration device; (j-4) A nanofiltration concentrated water pipe, one end of which is connected to the concentration side of the nanofiltration device and supplies the concentrated water of the nanofiltration device to the evaporator; (k-4) Permeate water piping, one end of which is connected to the permeation side of the reverse osmosis membrane device; (l-4) Thin tetraalkylammonium hydroxide drainage treatment equipment, connected to the other end of the permeated water pipe; and (m-4) The permeated water return pipe is connected to the permeated water pipe and supplies permeated water to the liquid tank, The cleaning system supplies the fresh tetraalkylammonium hydroxide solution to the tank, and circulates the fresh tetraalkylammonium hydroxide solution from the (a-4) to (e-4) and (f-4) To the circulatory system formed by (i-4) and the circulatory system formed by (a-4) to (c-4), (k-4) and (m-4), thereby Clean the reverse osmosis membrane of the reverse osmosis membrane device. For example, the tetraalkylammonium hydroxide-containing liquid treatment system of item 3 of the scope of patent application has: (a-5) Liquid tank for storing liquid containing tetraalkylammonium hydroxide; (b-5) Liquid supply piping, one end of which is connected to the liquid discharge side of the liquid tank; (c-5) Reverse osmosis membrane device (Y), connected to the other end of the liquid supply pipe; (d-5) Concentrated water piping, one end of which is connected to the concentration side of the reverse osmosis membrane device and supplies the concentrated water of the reverse osmosis membrane device to the evaporator; (e-5) Concentrated water return piping, which is connected to the concentrated water piping and supplies the concentrated water of the reverse osmosis membrane device (Y) to the liquid tank; (f-5) Permeate water pipe (P), one end of which is connected to the permeation side of the reverse osmosis membrane device (Y); (g-5) Permeated water tank, arranged in the middle of the permeated water pipe (P); (h-5) Dilute tetraalkylammonium hydroxide drainage treatment equipment, arranged at the other end of the permeated water pipe (P); (i-5) The permeated water return pipe (I) is connected to the permeated water pipe (P) between the reverse osmosis membrane device (Y) and the permeated water tank, and the reverse osmosis membrane device (Y) Permeated water is supplied to the liquid tank; (j-5) The permeated water concentration tank is arranged in the middle of the permeated water return pipe (I); (k-5) Another permeated water return pipe (II), which is branched from the permeated water pipe (P) between the permeated water tank and the thin tetraalkylammonium hydroxide drainage treatment equipment, and is connected to The permeated water return pipe (I) between the reverse osmosis membrane device (Y) and the permeated water concentration tank; (l-5) Another reverse osmosis membrane device (Z) is arranged in the middle of the other permeated water return pipe (II); (m-5) The nanofiltration device is arranged in the middle of the other permeated water return pipe (II) and treats the concentrated water of the other reverse osmosis membrane device (Z); (n-5) Another permeate pipe (Q), which connects the permeate side of the other reverse osmosis membrane device (Z) and the thin tetraalkylammonium hydroxide drainage treatment equipment; and (o-5) Nanofiltration concentrated water piping, connect the concentration side of the nanofiltration device and the other permeated water piping (Q), The cleaning system supplies the permeated water of the reverse osmosis membrane device (Y) to the liquid tank by concentrating the permeated water of the reverse osmosis membrane device (Z) and further passing through the nanofiltration device (Z), and The permeate treated water is in the circulation system formed by (a-5) to (d-5) and (e-5) and from (a-5) to (c-5), (f-5) Circulate in the two circulation system of the circulation system formed by (i-5), thereby cleaning the reverse osmosis membrane of the reverse osmosis membrane device. For example, the treatment system for tetraalkylammonium hydroxide-containing liquid in any one of items 4 to 8 of the scope of patent application has: A measuring device that measures the resist concentration of the cleaning solution supplied from the liquid tank by the cleaning system; and The cleaning state detection device detects the cleaning state from the measured resist concentration. A treatment method for tetraalkylammonium hydroxide containing liquid, comprising: When the liquid to be treated containing tetraalkylammonium oxide is concentrated by an evaporator, the liquid to be treated is concentrated by the reverse osmosis membrane device arranged in the front stage of the evaporator on the concentration side, The processing method of the tetraalkylammonium hydroxide containing liquid further includes: in response to the blockage of the reverse osmosis membrane of the reverse osmosis membrane device, using fresh tetraalkylammonium hydroxide liquid and/or permeation generated by the reverse osmosis membrane device The washing step of washing the reverse osmosis membrane with water.

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